ES2277381T5 - Preparation of vinyl containing macromers - Google Patents

Abstract

THE INVENTION REFERS TO POLYMERIC COMPOSITIONS OF INTEREST INCLUDING OLEFIN POLYMER CHAINS WITH A SUB, N M OF APPROX. 400 TO 75,000, A RATIO OF VINYL GROUPS TO TOTAL OLEFIN GROUPS ACCORDING TO FORMULA (1), WHERE A = -0.24 AND B = 0.8, AND WHERE THE TOTAL NUMBER OF VINYL GROUPS PER 1000 CARBON ATOMS IS HIGHER OR EQUAL TO 8000 / MN. THE INVENTION INCLUDES A PROCEDURE FOR PREPARING SAID POLYMERIC PRODUCTS WHICH CONSISTS OF CONTACTING ONE OR MORE OLEFIN COMMONOMERS WITH A CATALYST SYSTEM CONTAINING A TRANSITIONAL METAL CATALYST COMPOUND AND A TRANSITIONAL ALUMINUM TO ALUMINUM, WHERE THE TRANSITIONAL ALUMINUM IS INCLUDED BETWEEN 10: 1 AND LOWER OR EQUAL TO 220: 1 (AL: ME). THE CONDITIONS OF THE PROCEDURE OF THE INVENTION ALLOW TO OBTAIN PREDICTABLE MACROMER CATACTERISTICS, BOTH FOR MOLECULAR WEIGHT AND FOR VINYL INSATURATION.

Description

Preparation of vinyl containing macromers

Field of the Invention

The present invention relates to vinyl-containing macromers prepared from olefins using transition metal catalyst compounds with cocatalyst activators of the alumoxane type.

Background of the invention

It is known that polymers with terminal vinyl, including oligomers, homopolymers and copolymers for the purpose of this application, synthesized from two or more monomers, are useful for post-polymerization (or post-oligomerization) reactions due to the ethylenic unsaturation available in a polymer, either at one end of the chain or both. Such reactions include addition reactions, such as those used to graft other ethylenically unsaturated moieties, and additional insertion polymerization in which the polymers with terminal vinyl are copolymerized with other monomers such as α-olefins and / or other insert polymerizable monomers. In the latter case, polymers with terminal vinyl are often called macromonomers or macromers.

Previous work with metallocene catalyst compounds of transition metals activated with alkylalumoxanes such as methylalumoxane have led us to observe that their use in olefin polymerization gave rise to unsaturated terminal groups in polymers produced in a higher percentage than in those that had typically been obtained by Insertion polymerization using Ziegler-Natta catalysts prior to those of metallocene. See European patent EP-A-0 129 638 and its equivalent, US Pat. 5,324,800. The subsequent work of Resconi, et al, reported in Olefin Polymerization at Bis (pentamethylcyclopentadienyl) zirconium and -hafnium centers: Chain-Transfer Mechanisms, J. Am. Chem. Soc., 1992, 114, 1025-1032, resulted in the observation that the use of bis (pentamethylcyclopentadienyl) zirconcene or hafnocene in the oligomerization of propylene favors the elimination of methyl in β more than the most commonly expected elimination of hydride in β as a means for chain transfer, or polymer chain termination . This is based on the observation that the ratio of vinyl terminal groups and vinylidene terminal groups was in the range of 92 to 8 for zirconocene and 98 to 2 for hafnocene.

In addition to these observations, international patent application WO 94/07930 addresses the advantages of including long chain branches in polyethylene by incorporating terminal vinyl macromers in polyethylene chains when the macromers have critical molecular weights greater than 3,800, or, in other words contain 250 or more carbon atoms. The conditions that favor the formation of polymers with terminal vinyl are said to be higher temperatures, the absence of comonomers, the absence of transfer agents and a process without dissolution or a dispersion using an alkane type diluent. It is also said that an increase in temperature during polymerization results in the product of elimination of the hydride in β, for example if ethylene is added to form an "end capped" ethylene. This document continues to describe a large class of both mono-cyclopentadienyl and bis-cyclopentadienyl metallocenes suitable according to the invention when activated both by alumoxanes and by ionizing compounds that provide non-coordinating, stabilizing anions. All examples illustrate the use of the Lewis tris (perfluorophenyl) boron acid activator with bis (cyclopentadienyl) zirconium dimethyl at a polymerization temperature of 90 ° C. The copolymerization was carried out with ethylene and the two macromers, respectively, using the same catalyst systems used to form the macromers.

Branched ethylene macromers are described in international patent application WO 95/11931. According to this description the vinyl groups must be more than 75 mol%, more preferably more than 80 mol%, of the total unsaturated groups, and it is said that the weight average molecular weight is in the range of 100 to 20,000. The manufacturing method of the described macromers is said to be with a transition metal compound containing metals from groups 3 to 10, it is said that the cyclopentadienyl derivatives of groups 4, 5 and 6 are useful in this regard. It is also said that these transition metal compounds are capable of forming ionic complexes suitable for polymerization by reaction with ionic compounds, alumoxanes or Lewis acids. The ratio of the transition metal component to the alumoxane type component is said to be preferably 1/10 to 1 / 10,000, or most preferably 1/30 to 1/2000. Examples 1 and 7 illustrate the preparation of ethylene macromer with ratios between alumoxane type compound and transition metal compound of 240 and 2000, respectively.

Several patents address the use of metallocene catalysts with varying levels of alumoxane activating cocatalysts. One of them is US Pat. 4,752,597 in which relatively insoluble solid products in hydrocarbon compounds, reaction products of metallocenes and alumoxane, are prepared by reacting both in a suitable solvent with the molar ratios of aluminum metal to metal transition between 12: 1 and 100: 1 . Then the solid reaction product is removed. This solid reaction product is said to be useful in gas phase, suspension and solution polymerizations.

Another part of the technique addresses the preparation of polymers with terminal unsaturations with different metallocenes in different conditions, for unsaturation of the vinyl-, vinylidene-, vinyl- and trisubstituted-type as a result of the processes described. The difficulty in determining by standard characterization methods (1H-NMR or 13C-NMR) the total saturated chain terminations has resulted in the acceptance of unsaturated terminal groups by the fraction of the total of each type of unsaturation versus total unsaturated terminations. However, industrially effective production methods would benefit greatly from high concentrations of unsaturated terminal groups versus total terminal groups, that is, including saturated terminations. Thus, the variations described in molecular weight distributions and the inability to determine or predict exactly the type of resulting chain terminations, or the less favored production of unsaturated chain terminations other than vinyl, limits the utility of the prior art. It is generally accepted that vinyl chain terminations are more reactive with terminal functionalities and on insertion in subsequent polymerization reactions than the other types and are much more preferred. Therefore, further research was carried out to improve the process of preparing polymers with terminal vinyl, its predictability and its usefulness for use in the preparation of branched polymers.

Compendium of the invention

The invention comprises an olefin polymerization reaction product having an olefinic unsaturation that is predominantly vinyl. In these reaction product compositions the molar concentration of vinyl groups is greater than or equal to 50% of the total molar concentration of polymer chains. More specifically, as calculated by gel permeability chromatography (GPC) and refractive index difference (DRI) measurements, the invention is a polymeric reaction product composition of matter comprising ethylene polymer chains, which are copolymers in which the comonomer is C3-C12 α-olefin, and the ethylene polymer chains have a number average molecular weight ("Mn") of 1500 to 50,000, a molecular weight distribution by gel permeability chromatography (145 ° C) and a refractive index difference of 2 to 4, a ratio of vinyl groups to total olefinic groups according to the formula:

(1) vinyl groups ≥ [mole percent of comonomer ÷ 0.1] a x 10a x b

olefinic groups

in which, a = -0.24 and b = 0.8, and in which the total number of vinyl groups per 1000 carbon atoms is greater

or equal to 8000 ÷ Mn, taking the measurements of vinyl groups by gel permeation chromotography (145 ° C) and 1 H-NMR (125 ° C), the polymer chains of ethylene can be obtained by a method that involves contacting one or more monomers of olefin with a catalyst solution composition containing a transition metal catalyst compound and an alumoxane where the ratio between aluminum and transition metal is from 10: 1 to 100: 1.

A surprisingly, highly effective method for preparing polymers having high levels of vinyl unsaturation comprises contacting one or more olefinic monomers with a catalyst solution composition containing a transition metal catalyst compound and an alumoxane in which the ratio between aluminum and transition metal is from 10: 1 to 100: 1. A yield of vinyl-containing chains can be achieved at levels greater than 70% of the total unsaturated chains and simultaneously a higher yield of unsaturated chains can be achieved in the total polymer chains as calculated by GPC and NMR. In this way, the use of these process conditions allows predictable macromer characteristics to be obtained both in molecular weight and in vinyl unsaturation which also allow the preparation of branched polymers having adapted characteristics suitable for improved processing applications, for example when It requires, or industrially preferred, melt processing, and in polymer blends in which the choice of monomer constituents or macromer comonomers can lead to better compatibility or other characteristics of the polymer blend.

The invention also provides a branched polymer comprising branches derived from ethylene polymer chains, which are copolymers in which the comonomer is C3-C12 α-olefin, and the ethylene polymer chains have an Mn of 1500 to 75,000 and a ratio from vinyl groups to total olefinic groups according to the formula:

(1) vinyl groups ≥ [mole percent of comonomer ÷ 0.1] a x 10a x b

    olefinic groups

in which a = -0.24 and b = 0.8 and that has a total number of vinyl groups per 1000 carbon atoms that is greater than or equal to 8000 ÷ Mn.

A method of producing the branched polymer comprises

i) contacting one or more olefinic monomers with a catalyst solution composition containing a transition metal catalyst compound and an alumoxane in which the ratio between aluminum and transition metal is from 10: 1 to 220: 1 thus preparing polymers that have high levels of vinyl unsaturation; Y

ii) add the product of step i) in an insert polymerization environment with a catalyst compound capable of incorporating volume monomer.

Brief description of the drawings

FIG. 1 illustrates examples 1-24 of the application showing the vinyl yield as a percentage of the total olefinic groups in the polymer products and their ratio according to the following formula (i). Vinyl groups were characterized according to the 1 H (NMR) methods as described in the application.

Detailed description of the invention

The polymeric macromer compositions related to the invention are the polymer chain reaction products resulting from the polymerization by insertion or coordination of olefinic monomers. Means for achieving high proportions of chains containing vinyl in relation to the total number of unsaturated chains in the polymerization reaction products were efficiently achieved, levels greater than 80% of chains containing vinyl were reached, and even greater than 90% . For copolymers the amount of vinyl chains depended on the ratio of ethylene and comonomer as defined in equation (I). Polymeric compositions or reaction products contain chains with narrow polydispersities, 2 to 4 or even 2 to 3.5.

In the formula (I) above, the values of a and b are within the preferred ranges expressed in Table A.

Table A

to

b

-0.20

0.8

-0.18

0.83

-0.15

0.83

-0.10

0.85

The total number of vinyl groups per 1000 carbon atoms of the polymeric reaction product is typically greater than 0.13 and less than 9.85.

The polymer compositions discussed in this report thus show a greater number of vinyl-containing chains as a total polymeric reaction product, including both polymeric chains having saturated groups and those with unsaturated groups. Therefore, these polymeric products can be used effectively for subsequent reactions in which reactive vinyl groups are needed. A measure of this efficacy of the polymer products of the invention is illustrated by the observed reaction efficiencies, which produce the reaction products sought in functionalized reactions or macromer copolymerization reactions. The higher the overall content of vinyl groups, the higher the performance of functionalized polymer or the performance of copolymers that continue macromer branches.

A wide range of polymeric reaction products of the invention containing vinyl macromers, can be synthesized using the catalyst compositions of the present invention. Thus, the polymerized monomers using these catalysts are ethylene and C3-C12 α-olefins. As this list suggests, any comonomer copolymerizable with ethylene by coordination or insertion polymerization will be suitable according to the invention. This also includes: internal olefins, such as 1-butene; substituted olefins, such as 3-methyl-1pentene; olefins with multiple substitutions, such as 3,3-dimethyl-1-hexene and aromatic olefins. The binding of monomers in polymeric reaction products is not limited to random copolymers or mixtures of random copolymers. It is known in the art that the sequence of monomers and comonomers in the chains can be controlled to communicate useful properties using different means, for example, flux catalysts or sequential polymerization processes.

The method of preparing the vinyl-containing macromer polymeric product of the invention involves contacting the monomers with a catalyst dissolution composition containing a transition metal catalyst compound and an alumoxane in a preferred ratio between aluminum and transition metal. The catalyst solution preparation typically comprises contacting the alumoxane type activator with the transition metal compound in a suitable solvent to form an activated catalyst solution. A preferred solvent for the catalyst solution is toluene, in view of the high solubility of alumoxane and many

of the transition metal compounds that are suitable as catalysts when activated therein. Other solvents capable of solvating to a significant degree both the activator and the transition metal compound, as can be readily determined empirically, are also suitable. Both aliphatic and aromatic solvents will be suitable, while the transition metal compound and the alumoxane activator are substantially soluble at the mixing temperatures used.

The method of preparing the vinyl-containing macromer polymeric product of the invention depends mainly on the molar relationship between the aluminum of the alumoxane alkyl activator and the transition metal. Preferably this level is ≥ 20 and ≤ 175; more preferably ≥ 20 and ≤ 140; and, most preferably ≥ 20 and ≤ 100. The temperature, pressure and reaction time depend on the selected process but are generally within the normal ranges for the selected process. Thus the temperatures may be in the range of 20 ° C to 200 ° C, preferably 30 ° C to 150 ° C, more preferably 50 ° C to 140 ° C, and most preferably between 55 ° C and 135 ° C. Reaction pressures can generally vary from atmospheric to 305x103 kPa, preferably 182x103 kPa. For typical dissolution reactions, temperatures will typically be in the range from room temperature to 250 ° C with pressures from room to 3450 kPa. The reactions can be carried out in batches. The conditions for suspension type reactions are similar to the conditions in solution except that the reaction temperatures are limited to the melting temperature of the polymer. In some reaction configurations, a supercritical fluid medium with temperatures up to 250 ° C and pressures up to 345x103 kPa can be used. Under high temperature reaction conditions, macromer products with low molecular weight ranges are typically produced.

Batch reaction times may vary from 1 minute to 10 hours, more preferably from 5 minutes to 6 hours and most typically from 45 minutes to 90 minutes. The reactions can also be carried out continuously. In continuous processes, the average residence times may vary similarly from 1 minute to 10 hours, more preferably from 5 minutes to 6 hours and most typically from 45 minutes to 90 minutes.

Suitable transition metal catalysts in the process for preparing reaction products containing vinyl macromers include one or more transition metal catalyst precursor compounds having both 1) stabilizing auxiliary ligands and 2) additional ligands that react with the alumoxane activators such that an active transition metal catalyst complex is produced. Preferred compounds include metallocene compounds containing at least one auxiliary substituted or unsubstituted cyclopentadienyl ("Cp") ring as a transition metal ligand. In this substituted memory means that one

or more of the hydrogen atoms attached to the carbon atoms of one or both Cp rings is substituted by one or more monovalent radicals capable of forming a sigma bond with the ring carbon. Examples include C1-C30 hydrocarbyl radicals and their homologs in which one or more carbon atoms is substituted with another atom of group 14, e.g. eg, Yes or Ge. The term "substituted" includes both 1) radicals that form bridge bonding or binding radicals that are attached to two different Cp ligands or to a Cp ligand and another transition metal ligand such as a heteroatom ligand of Group 15 or 16, as well as 2 ) condensed ring configurations in which two atoms of the Cp ring are covalently linked by substituents such as indenyl and fluorenyl ligands, which in turn can be further substituted and / or linked by bridges. Examples include those compounds of Groups 4-6 and monocyclopentadienyl and biscyclopentadienyl known to those skilled in the art as suitable for the polymerization of olefins. For biscyclopentadienyl compounds see, p. e.g., U.S. Pat. 5,324,800, 5,324,801, 5,441,920 and 5,502,124. For exemplary monocyclopentadienyl metallocene compounds see, p. e.g., U.S. Pat. 5,055,038, 5,264,505, and U.S. Pat. in process with us 08 / 545,973, filed on October 20, 1995 and 08 / 487,255 filed on June 7, 1995 and published as international patent application WO 96/00244.

Additionally, those for cyclopentadienyl analogs in the one or more carbon atoms of the ring are substituted with a heteroatom of Group 14 or 15, or in condensed ring systems, such as indenyl, are included in the definition of metallocene and flourenyl, in which one or more carbon atoms of any of the condensed rings is substituted in this way. A list of suitable metallocenes includes essentially any of those available in the patent literature, such as those listed above, and in the academic literature regarding the polymerization of olefins, specifically including those dealing with amorphous homopolymers and copolymers, and semicrystalline and crystalline of more than one monomer. In particular, suitable documents contain those documents that deal with polymers and copolymers of polyethylene and those that deal with higher stereoregular olefins, such as polymers and copolymers of isotactic and syndiotactic polypropylene.

Also suitable are any of the other transition metal olefin polymerization catalyst precursor compounds, particularly those of Groups 4, 5, 6, 7, 8, 9 and 10, known in the art for being able to activate with alumoxane, see for example international patent application WO 96/23010, US Pat. 5,504,049, 5,318,935, and US Series Nos. in process with the present 08 / 473,693, filed on June 7, 1995, and 60/019626, filed on June 17, 1996.

Suitable reactor configurations for the present invention include continuous, batch and semi-batch reactors. The dissolution phase, suspension phase and supercritical phase conditions are useful for the polymerization of olefins using these catalysts. Additionally, they are explicitly contemplated

combinations of the above reactor types in multiple series of reactors and / or multiple reaction conditions and / or multiple catalyst configurations.

Preferred solvents for dissolution phase reactions are selected according to polymer solubility, volatility and safety / health considerations. Alkanes or non-polar aromatic compounds are preferred. For supercritical fluid reactions, the reaction medium is generally composed of polymer, monomer and comonomer with, optionally, suitable supercritical co-solvents. For suspension reactions the diluent may be an inert liquid or a massive liquid comonomer. Solvents, co-solvents and comonomers are typically purified by treatment with an absorbent material including aluminas and molecular sieves. Impurities can also be deactivated by the addition of suitable inactivators well known in the art, including but not limited to metal alkyls and alumoxanes.

INDUSTRIAL UTILITY

Branched polymers in which at least some of the branching are derived from the product containing vinyl macromers of the invention will be particularly useful, for example, for better processing ethylene copolymers having branching offspring of the macromer. The incorporation of a vinyl macromer for the preparation of branched polymers can be achieved by adding the polymer product of the invention in an insert polymerization environment with a catalyst compound capable of incorporating volume monomer. This includes the mono-and biscylopentadienyl metallocene catalyst compounds linked by bridge, suitable for insertion polymerization of such volume comonomers such as 1-octadecene, 3-methyl-1-pentene and cyclic olefins, such as norbornene. See, for example, US Pat. 5,324,801, 5,444,145, 5,475,075 and

5,635,573 and international patent application WO 96/000244. Other suitable catalyst systems include, but are not limited to, amido and imido derivatives of metals of Groups 4, 5, 6, 7, 8, 9 and 10 described in the documents noted above for polymeric products containing vinyl macromer of the invention. Also, the international patent application WO 94/07930, discussed in the background, describes the advantages of incorporating macromers and means for doing so.

For the preparation of both the vinyl macromer product and the branched copolymer, it is known that many methods and changes are possible in the order of adding the macromer and monomer species to the reactor, some more advantageous than others. For example, it is widely known in the art that prior activation of metallocene with alumoxane prior to the addition to a continuous reactor in the dissolution phase produces activities greater than the continuous addition of the metallocene and the activator in two separate streams. In addition, it may be advantageous to control the prior contact time to maximize catalyst efficiency, e.g. eg, avoiding excessive aging of the activated catalyst composition.

Preferred branched copolymers of the invention are copolymers of ethylene with two or more comonomers. The most readily available comonomers are especially propylene, 1-butene, isobutylene, 1-hexene and 1octene. Other suitable comonomers include but are not limited to: internal olefins, cyclic olefins, substituted olefins, multi-substituted olefins and aromatic olefins. The selection of the comonomers that are used is based on the desired properties of the polymer product and the metallocene employed will be selected for its ability to incorporate the desired amount of olefins. See US Pat. 5,635,573 describing various metallocenes suitable for ethylene-norbornene copolymers and US patent application. in process with the present with serial number 08 / 651.030, filed on 5/21/96, which describes monocyclopentadienyl metallocenes suitable for ethylene-isobutylene copolymers.

For better tearing of polyethylene films, a longer olefin comonomer, such as 1-octene, may be preferred, rather than a shorter olefin such as butene. For better elasticity or barrier properties of a polyethylene film, a cyclic comonomer such as norbornene over an olefin may be preferred. The comonomer concentrations in the reactor will be selected to provide the desired amount of comonomer to the polymer, most preferably from 0 to 50 mole percent.

In addition, it is possible to react two or more macromer polymer chains having the same or different comonomers and / or the same or different molecular weights to derive the new polymer compositions with desirable properties. The authors of the invention have found that statistical mixtures of formulated mixtures of branched / block molecules derived from the binding of these macromer chains show commercially useful properties. Optionally, it is possible to use dienes to control the incorporation of unsaturated chains into other unsaturated chains.

Functionalization reactions for low molecular weight polymer products containing vinyl include those based on thermal or free radical addition, or grafting, of compounds containing the vinyl group and ethylenically unsaturated compounds. A typical, industrially useful example is successive grafting reactions with maleic acid, maleic anhydride or vinyl acids or acid esters, e.g. eg, acrylic acid, methyl acrylate, etc. The addition of these groups allows further functionalization by amidation, immidization, esterification and the like. For example, see US Pat. 5,498,809 and international patent applications WO 94/19436 and WO 94/13715. Each of them addresses ethylene-1-butene polymers that have terminal vinylidene and its functionalization in effective dispersants in lubricating oil compositions. See

also European patent EP 0 513 211 B1 in which similar copolymers are described in effective compositions that modify wax crystals for fuel compositions. The polymeric products of the invention useful in this aspect will typically have an Mn of about 1,500 to 10,000 Mn preferably about 2,000 to 5,000 Mn.

It is preferable to use the polymeric products with high vinyl unsaturation of the invention so that it is functionalized or copolymerized immediately after its preparation. Very reactive vinyl groups appear to be susceptible to reactions of by-products with adventitious impurities and even dimerization or addition reactions with other polymer chains containing unsaturated groups. Thus, maintenance in a cooled environment, inert in dilute concentrations after preparation and rapid subsequent use will optimize the effectiveness of the use of the macromer product of the invention. A continuous process using reactors in series, or reactors in parallel will thus be effective, the vinyl macromer product being prepared in one and continuously introduced in the other.

EXAMPLES

General: All polymerizations were carried out in a 1-liter Zipperclave reactor equipped with a water jacket to control the temperature. Liquids were measured inside the reactor using calibrated sight glasses. The hexane, toluene and butene feeds of high purity (> 99.5%) were purified by first passing them through basic alumina activated at high nitrogen temperature, followed by a 13x molecular sieve activated at high nitrogen temperature. Quality ethylene for polymerization was supplied directly in a nitrogen jacket line and was used without further purification. 10% Methyllumoxane (MAO) in toluene, transparent was received from Albemarle Inc. in stainless steel cylinders, divided into 1 liter glass containers and stored in a laboratory glove box at room temperature. Ethylene was added to the reactor as necessary to maintain the total system pressure at the levels described (semi-batch operation). The ethylene flow rate was controlled using a Matheson mass flow meter (model number 8272-0424). To ensure that the reaction medium was well mixed, a flat blade stirrer rotating at 750 rpm was used.

Preparation of the reactor: First the reactor was cleaned by heating it to 150 ° C in toluene to dissolve any polymer residue, then cooled and emptied completely. Subsequently, the reactor was heated using jacket water to 110 ° C and the reactor was purged with a nitrogen flow for a period of ~ 30 minutes. Prior to the reaction, the reactor was further purged using 10 cycles of nitrogen at pressure / air (at 791 kPa (100 psi)) and 2 cycles of ethylene at pressure / air (at 2170 kPa (300 psi)). The cycles serve three purposes: (1) to fully penetrate all dead ends such as pressure gauges and purge fugitive contaminants,

(2) displace nitrogen from the system with ethylene, and (3) make a pressure test to the reactor.

Catalyst Preparation: All catalyst preparations were carried out in an inert atmosphere with a content of <1.5 ppm H2O. To measure exactly small amounts of catalyst, often less than one milligram, methods for reserving the freshly prepared catalyst in solution / dilution were used to prepare the catalyst. To maximize the solubility of the metallocenes, toluene was used as the solvent. The stainless steel transfer tubes were washed with MAO to remove impurities, emptied and the activator and catalyst, first the MAO, were added with a pipette.

Macromer Synthesis: First, the catalyst transfer tube was attached to a reactor inlet with a continuous flow of nitrogen to purge the ambient air. Subsequently, the reactor was purged and a pressure test was performed as summarized above. Then, 600 ml of solvent was charged into the reactor and heated to the desired temperature. The comonomer was then added (if applicable), the temperature was allowed to equilibrate, and the base pressure of the system was recorded. The desired partial pressure of ethylene was added above the base pressure of the system. After allowing ethylene to saturate the system (as indicated by a zero flow of ethylene), the pulse-shaped catalyst was injected using high pressure solvent. The progress of the reaction was monitored by reading the ethylene absorption of the electronic mass flow meter. When the desired amount of macromer had accumulated, the flow of ethylene was cut off and the reaction was stopped by rapid cooling (~ 1 minute) and the addition of excess methanol to precipitate the polymer product. The polymer / solvent mixture was dried in a flow of ambient air.

Product characterization: Polymer product samples were analyzed by gel permeability chromatography using a 150 ° C high temperature Waters system equipped with a DRI Detector, a Showdex AT-806MS column and operating the system at a temperature of 145 ° C. The solvent used was 1,2,4-trichlorobenzene, with which sample polymer solutions of 0.1 mg / ml concentration were prepared for injection. The total solvent flow rate was 1.0 ml / minute and the volume injected 300 microliters. GPC columns were calibrated using a series of narrow distribution polystyrenes (obtained from Tosoh Corporation, Tokyo, 1989). For quality control, a standard width calibration based on linear PE samples NBS-1475 was used. The standard was eluted with each 16-vial car. It was injected twice, as the first sample of each batch. After elution of the polymer samples, the resulting chromatograms were analyzed using the Waters Expert Fuse program to calculate the molecular weight distribution and one or more averages of Mn, Mw and Mz. The quantification of long chain branching was carried out by the method of Randall, Rev. Macromo. Chem. Phys., C29, (2 & 3), p. 285-297. 1H-NMR analyzes were performed using a Varian Unity model

500mHz operating at 125 ° C using d2-tetrachloroethane as solvent. 13C-NMR analysis was performed using a 100mHz frequency Varian Unity Plus model, under the same conditions.

Example 1.

Catalyst Preparation A stainless steel catalyst addition tube was prepared as summarized above. A 0.25 milliliter aliquot of a 10% methylalumoxane (MAO) solution in toluene was added, followed by 0.5 milliliters of a toluene solution containing 1 milligram of Cp2ZrCl2. bisciclopentadienyl zirconium dichloride, per milliliter. The sealed tube was removed from the glove box and connected to a reactor inlet with a continuous flow of nitrogen. A flexible, stainless steel line that starts from the multiple supply of the reactor was connected to the other end of the addition tube with a continuous flow of nitrogen.

Homopolymerization The reactor was purged with nitrogen and checked for pressure simultaneously by two filling cycles with ethylene / purge (up to 2170 kPa (300 psig)). Then, the reactor pressure was raised to ~ 377 kPa (40 psig) to maintain a positive pressure in the reactor during the adjustment operations. The water jacket temperature was set at 90 ° C and 600 milliliters of toluene was added to the reactor. The stirrer was set at 750 rpm. Additional ethylene was added to maintain a positive manometric pressure in the reactor as ethylene was absorbed in the gas phase in the solution. The reactor temperature controller was set at 90 ° C and the system was allowed to reach a steady state. The ethylene pressure regulator was set close to 791 kPa (100 psig) and ethylene was added to the system until a steady state measured as zero ethylene absorption was reached. The reactor was isolated and a pulse of toluene was used at a pressure of 2170 kPa (300 psig) to pass the catalyst solution from the addition tube to the reactor. The multiple supply of ethylene at 791 kPa (100 psig) was immediately opened to the reactor to maintain a constant pressure in the reactor as ethylene was consumed in the reaction. After 30 minutes of reaction, the reaction solution was cooled rapidly and 200 milliliters of methanol was added to stop the reaction and precipitate the polymer. The product was removed in a 2 liter open bucket and dried in ambient air, yielding 38 grams of homopolyethylene. A summary of the reaction conditions of Example 1 is given in Table 1.

Examples 2-7.

Catalyst Preparation The Cp2ZrCl2 catalysts activated with MAO of Examples 2-7 were identical to those of Example 1 except that the amounts of catalyst solution (containing 1 milligram of Cp2ZrCl2 per milliliter of toluene) and the amounts of MAO solution at 10 % in toluene used were different. These catalyst formulations are summarized in Table 1.

Homopolymerization The reaction conditions used in Examples 2-7 involved only minor modifications of the conditions used in Example 1. These variations are summarized in Table 1.

Example 8

Catalyst Preparation The catalysts were prepared in a manner analogous to that of Example 1, differing only in the amounts of Cp2ZrCl2 and MAO activator used. These catalyst preparations are summarized in Table 1.

Copolymerization The reactor was prepared as in Example 1 except that nitrogen was used to fill the reactor before the addition of liquids. After the addition of toluene, 50 milliliters of butene was added and the reactor temperature was allowed to equilibrate to 90 ° C. A base pressure of 273 kPa (25 psig) was recorded. Ethylene was added to bring the total system pressure in equilibrium to 963 kPa (125 psig), or whatever is established alternately, to produce a partial ethylene pressure of 688 kPa (100 psia). 10 minutes after catalyst injection, the reaction was stopped by cooling and adding methanol. 64 grams of ethylene / butene copolymer were isolated after drying.

Examples 9-10.

Catalyst Preparation The amounts of Cp2ZrCl2 catalyst and MAO activator used in Examples 9-10 are summarized in Table 1. The addition tubes and catalyst solutions were prepared using the methods of Example 1.

Copolymerization Following the methods of Example 8, nitrogen, solvent and butene were added to the reactor and heated to 90 ° C. The base pressure was recorded and the ethylene pressure regulator was set to add ethylene so that the equilibrium partial pressure of ethylene was raised to 689 kPa (100 psia). After saturating the system with ethylene (measured as zero absorption of ethylene), the catalyst was injected. The reaction was stopped by the addition of methanol after the times in Table 1 elapsed.

Example 11

Catalyst Preparation An aliquot of 2.5 milliliters of 10% MAO in toluene was added to the stainless steel catalyst addition tube prepared as above. Then, they were added to the addition tube 2

milliliters of a toluene solution containing 0.5 milligrams of (C5Me4SiMe2NC12H23) TiCl2 (tetramethylcyclopentadienyl) dimethylsilyl (cyclododecamide) titanium dichloride, per milliliter.

Homopolymerization The polymerization was performed using essentially the same procedures as in Example 1, except that the conditions specified in Table 1 were used. After drying, 17 grams of homopolymer were obtained.

Examples 12-15.

Catalyst Preparation The catalyst and activator were prepared using the procedures of Example 11. Only the amounts of MAO catalyst and activator solution were different (see Table 1).

Homopolymerization The procedures used in Examples 12-15 were identical to those in Example 11, but with slightly different conditions summarized in Table 1.

Examples 16-19.

Catalyst Preparation The catalyst and activator were prepared using the methods of Example 11. See Table 1 for the amounts of activator and catalyst employed.

Copolymerization Solvent, followed by 1-butene, was added to a reactor filled with nitrogen. The reactor was heated to the desired reaction temperature (see Table 1) and the pressure was recorded. The ethylene supply regulator was adjusted to provide ethylene at a pressure necessary to maintain the absolute partial pressure of tabulated ethylene. The ethylene supply to the reactor was then opened until equilibrium was reached, as indicated by a zero flow of ethylene. The reactor was sealed and catalyst was injected using high pressure solvent (toluene or hexane, depending on the solvent used in the reaction). After the indicated reaction times, the product cooled rapidly, the reaction was stopped using methanol and dried in ambient air.

Examples 20-22.

Catalyst Preparation Toluene solutions containing 1 milligram of ((CH3) 2Si (C9H6) 2) HfCl2, dimethylsilyl bis (indenyl) hafnium dichloride, per milliliter of solution were added to 10% MAO solutions in toluene to formulate the catalyst. The quantities used are summarized in Table 1.

Copolymerization In the copolymerization reactions, methods identical to those used in Examples 16-19 were employed with the exception of Example 21c in which hydrogen was added to the reactor. Hydrogen was supplied as follows: Toluene and butene were added to a clean reactor containing nitrogen. The reactor was heated to 90 ° C and a pressure (base) of 308 kPa (30 psig) was recorded. Hydrogen was added so that the system pressure rose to 998 kPa (130 psig) (hydrogen partial pressure 689 kPa (100 psia)). Then, the ethylene regulator was set at 1687 kPa (230 psig), so that an ethylene partial pressure of 689 kPa (100 psia) was provided to the system. Then, the reaction was carried out analogously to Example 20.

Examples 23 & 24.

Catalyst Preparation Solutions in toluene of Cp2ZrCl2 and (C5Me4SiMe2NC12H23) TiCl2 described in Examples 1 and 11 were used respectively. MAO (10% in toluene) was added first to the catalyst addition tube, followed by a solution of (C5Me4SiMe2NC12H23) TiCl2 and subsequently by a solution of Cp2ZrCl2.

Homopolymerization Essentially the same procedures were used as in Example 1. Only the conditions were different (Table 1).

Polymer Analysis Table 2 describes the molecular weight, comonomer content, and structural distribution of the unsaturated groups of the reaction products. It was found that the concentrations of unsaturated groups (total olefins per 1000 carbon atoms) as well as the selectivity of the vinyl groups increased as the aluminum-metal ratio decreased, all other factors being equal. Olefin (comonomer) concentrations can be further increased by decreasing the concentration of ethylene in solution (decreasing the partial pressure of ethylene or increasing the temperature).

Table 1. Compendium of reaction conditions.

Ex.

Catalyst* Decatalyst amount (mg) Ethylene pressure kPa (psi) Temp. reaction (ºC) MAO ** (ml) Metal / Al Ratio Hexane (ml) Toluene (ml) 1-butene (ml) DehydrogenkPa Pres (psi) Time (min) Yield (g)

1 C

to 0.5 791 (100) 90 0.25 172 0 600 30 38

2 C

to 4 791 (100) 90 0.25 21.5 0 600 30 3. 4

3c

to 8 791 (100) 90 0.5 21.5 0 600 18 58

4c

to 32 239 (20) 90 2 21.5 0 600 30

5c

to 0.5 791 (100) 90 0.25 172 600 0 30 eleven

6c

to 8 791 (100) 90 0.5 21.5 600 0 30 19

7c

to 32 204 (15) 90 2 21.5 600 0 30 2

8c

to 0.5 791 (100) 90 0.25 172 0 600 fifty 10 64

9c

to one 791 (100) 90 0.5 172 600 0 fifty 30

10c

to 32 791 (100) 90 2 21.5 600 0 fifty 10 31

11c

b one 791 (100) 90 2.5 1375 0 600 30 17

12c

b 8 239 (20) 90 0.5 34.4 0 600 5

13c

b one 170 (10) 90 2.5 1375 600 0 30 12

Ex.

Catalyst* Decatalyst amount (mg) Ethylene pressure kPa (psi) Temp. reaction (ºC) MAO ** (ml) Metal / Al Ratio Hexane (ml) Toluene (ml) 1-butene (ml) DehydrogenkPa Pres (psi) Time (min) Yield (g)

14c

b 32 218 (17) 90 2 34.4 600 0 30

15c

b 10 308 (30) 90 6 1375 600 0 twenty

16c

b one 791 (100) 90 1.5 825 0 600 10 30 fifteen

17c

b one 791 (100) 90 1.5 825 0 600 fifty 30 22

18

b 16 791 (100) 90 one 34.4 0 600 10 30

19c

b one 791 (100) 90 2.5 1375 600 0 fifty 30 twenty-one

20c

C one 791 (100) 90 0.5 316 0 600 fifty 30 6.5

21c

C 5 998 (130) 90 1.25 158 0 600 fifty 791 (100) 30 36

22c

C one 791 (100) 90 0.5 316 600 0 fifty 30 5

23c

a + b 32 + 1.5 515 (60) 90 3 31.4 600 0 60 47

24c

a + b 1 + 1 308 (30) 90 one 212 0 600 30

* a - Cp2 ZrCl2 b - (C5 Me4 SiMe2 NC12H23) TiCl2 c - ((CH3) 2 (C9 H6) 2) HfCl2 ** MAO - 10% weight methylolumoxane in toluene

Table 2. Compendium of polymer analyzes.

Ex.

Mn Mw Mw / Mn % olefinasvinyl Vinyl for 1000 C Vinyl for 1000 C Vinylidene for 1000 C Trisubstituted by 1000 C % by mole debuteno % by weight debuteno LCU by 1000C

1 C

47184 101961 2,161 51.5 0.17 0.08 0.03 0.05

2 C

25154 55516 2,207 91.4 0.32 0.03 0 0

3c

24619 54085 2,197 94.6 0.35 0.02 0 0

4c

5657 14916 2,637 88.4 2.05 0.15 0.12 0

5c

39544 102041 2,580 76.0 0.19 0.04 0.02 0

6c

12933 46941 3,630 89.5 0.77 0.09 0 0

7c

1744 4710 2,701 85.4 10.16 0.36 0.74 0.63

8c

10222 35513 3,474 18.5 0.17 .0.08 0.02 0.65 44 85

9c

10315 33214 3,220 36.1 0.35 0.09 0.36 0.17 2 39

10c

6964 35992 5,168 64.3 2.96 0.06 0.07 1.51 3.9 75

11c

110000 332087 3,019

12c

22124 125359 5,666 89.6 0.43 0.03 0.02 0

13c

99900 288000 2,883

14c

3655 13117 3,589 86.1 2.48 0.12 0.11 0.17

Ex.

Mn Mw Mw / Mn % olefinasvinyl Vinyl for 1000 C Vinyl for 1000 C Vinylidene for 1000 C Trisubstituted by 1000 C % by mole debuteno % by weight debuteno LCU by 1000C

15c

14087 37966 2,695 64.3 0.36 0.10 0.05 0.05 0.21

16c

57187 134710 2,356 63.2 0.12 0.02 0.05 0

17c

62704 153163 2,443 14.3 0.03 0.07 0.01 0.1 35.9 52.8

18

48611 173905 3,577 84.6 0.22 0 0 0.04 5.8 10.9

19c

190105 402985 2,120 5.9 0.01 0.02 0 0.14 31.7 48.1

20c

81835 211882 2,589 6.7 0.02 0.09 0.05 0.14 16.8 28.7

21c

7014 23431 3,341 56.3 0.09 0.02 0.04 0.01 12.5 22.2

22c

63906 148475 2,323 14.6 0.06 0.11 0.06 0.18 16.1 27.7

23c

4396 17467 3,973 90.0 2.71 0.12 0.18 0

24c

27359 56997 2,083 59.3 0.32 0.16 0.03 0.03

The following examples illustrate the preparation of macromers and copolymerization thereof with copolymerizable monomers to form branched long chain copolymers.

Example I (comparative)

Catalyst Preparation A stainless steel catalyst addition tube was prepared as summarized above. A 1 milliliter aliquot of 10% methylalumoxane (MAO) solution in toluene was added, followed by 16 mg of Cp2ZrCl2 solution in toluene. The sealed tube was removed from the glove box and connected to a reactor inlet with a continuous flow of nitrogen. A flexible, stainless steel line that starts from the multiple supply of the reactor was connected to the other end of the addition tube with a continuous flow of nitrogen.

Synthesis of the macromer. The 1 liter reactor was purged with nitrogen and checked for pressure simultaneously by two filling cycles with ethylene / purge (up to 2170 kPa (300 psig)). Then, the reactor pressure was raised to ~ 239 kPa (20 psig) to maintain a positive pressure in the reactor during the adjustment operations. The water jacket temperature was set at 90 ° C and 600 milliliters of toluene was added to the reactor. The stirrer was set at 750 rpm. Additional ethylene was added to maintain a positive manometric pressure in the reactor as ethylene was absorbed in the gas phase in the solution. The reactor temperature controller was set at 90 ° C and the system was allowed to reach a steady state. The ethylene pressure regulator was set close to 239 kPa (20 psig) and ethylene was added to the system until a steady state measured as zero ethylene absorption was reached. The reactor was isolated and a pulse of toluene was used at a pressure of 2170 kPa (300 psig) to pass the catalyst solution from the addition tube to the reactor. The multiple supply of ethylene at 239 kPa (20 psig) was immediately opened to the reactor to maintain a constant pressure in the reactor as ethylene was consumed in the reaction. After 8 minutes of reaction, the reaction solution was rapidly heated to 150 ° C for 30 minutes to deactivate the catalyst, then cooled to 90 ° C. A small sample of macromer was removed through an addition opening. Analysis by 13C-NMR indicated that there were no measurable long chain branches present in the macromer. The average molecular weights in number and weight of the macromer were 9,268 and 23,587 Daltons, respectively, 81.7% being vinyl olefins.

Example II (comparative)

Preparation of branched polymer. 25 grams of 80.7% norbornene solution in toluene was added to the reactor contents of Example I immediately after taking samples of the macromer. A catalyst addition tube containing 0.5 ml of 10% MAO solution in toluene and 1 mg of CpCp * ZrCl2 was connected to the addition opening. The total pressure in the reactor at 90 ° C was raised to 791 kPa (100 psig) by adjusting the ethylene supply regulator and allowing the system to reach equilibrium, as indicated by a zero flow of ethylene in the reactor. The catalyst was injected using a pulse of toluene at 2170 kPa (300 psig). After 20 minutes of reaction time, the system was quickly discharged and cooled. The sample was quenched using excess methanol and evaporated to dryness. 42 grams of ethylene-norbornene copolymer product containing branched polymers with homopolyethylene branches and ethylene-norbornene main chain were isolated. Analysis with 13C NMR of the product indicated that branches with a chain length of 0.085 per 1000 carbon atoms were present.

Example III

Catalyst Preparation A stainless steel catalyst addition tube was prepared as summarized above. A 2 milliliter aliquot of 10% methylalumoxane (MAO) solution in toluene was added, followed by 32 mg of (C5Me4SiMe2NC12H23) TiCl2 solution in toluene. The sealed tube was removed from the glove box and connected to a reactor inlet with a continuous flow of nitrogen. A flexible, stainless steel line that starts from the multiple supply of the reactor was connected to the other end of the addition tube with a continuous flow of nitrogen.

Synthesis of the macromer. The 2 liter reactor was purged with nitrogen and checked for pressure simultaneously by two filling cycles with ethylene / purge (up to 2170 kPa (300 psig)). Then, the reactor pressure was raised to approximately 377 kPa (40 psig) to maintain a positive pressure in the reactor during the adjustment operations. The water jacket temperature was set at 90 ° C and 1200 milliliters of toluene and 20 ml of butene were added to the reactor. The stirrer was set at 750 rpm. Additional ethylene was added to maintain a positive manometric pressure in the reactor as ethylene was absorbed in the gas phase in the solution. The reactor temperature controller was set at 90 ° C and the system was allowed to reach a steady state. The ethylene pressure regulator was set close to 377 kPa (40 psig) and ethylene was added to the system until a steady state measured as zero ethylene absorption was reached. The reactor was isolated and a pulse of toluene was used at a pressure of 2170 kPa (300 psig) to pass the catalyst solution from the addition tube to the reactor. The multiple supply of ethylene at 377 kPa (40 psig) was immediately opened to the reactor to maintain a constant pressure in the reactor as ethylene was consumed in the reaction. After 25 minutes of reaction, the reaction solution was rapidly heated to 147 ° C for 15 minutes to deactivate the catalyst, then cooled to 90 ° C. The system was continuously discharged and purged with nitrogen until dry

so that both the solvent and the ethylene and butene monomers were removed. Then they were added

1,200 ml of toluene and the system was allowed to reach equilibrium at 90 ° C. It was removed to analyze a sample of the ethylene-butene macromer through the addition opening. The average molecular weights in number and weight of the macromer were 22,394 and 58,119 respectively. The comonomer content of the macromer obtained

5 by FTIR measurements it was 6.6% in moles of butene.

Example IV

Preparation of branched polymer. The reactor content of Example III (at 90 ° C) was subjected to pressure at 791 kPa (100 psig) by adjusting the ethylene supply regulator and allowing the system to reach equilibrium, as indicated by a zero flow of ethylene in the reactor. An addition tube of 10 catalyst containing 2 ml of 10% MAO solution in toluene and 2 mg of solution (C5Me4SiMe2NC12H23) TiCl2 in toluene was connected to the addition opening. The catalyst was injected using a pulse of toluene at 2170 kPa (300 psi). After 10 minutes of reaction time, the system pressure rose to 2170 kPa (300 psig). After 23 minutes of reaction time, the system was quickly discharged and cooled. The sample was quenched using excess methanol and evaporated to dryness. 69.5 grams of product were isolated and the analysis

15 by FTIR gave homopolyethylene main chains having 56% by weight of branches of the ethylene-butene macromer of Example III.

Chain branching was measured by separating the high molecular weight branched material from the low molecular weight macromer using GPC methods and then quantifying by FTIR the amount of butene both in the macromer and in the high molecular weight branched polymer. So the average butene content

20 in the branched, high molecular weight material was 3.7 mol%, as opposed to that of the macromer product with 6.6 mol% of butene. The branching level was calculated from the following equation:

Butene% in the high MW fraction

% by weight of branches = x 100%

 % butene in the macromer fraction

Table 1. Compendium of reaction conditions.

Ref.

Catalyst* Decatalyst amount (mg) Partial pressure of ethylene kPa (psi) Temp. reaction (ºC) MAO ** (ml) Metal / Al Ratio Toluene (ml) 1-Butene (ml) Norbornene (at 80.7% in toluene) Time (min) Yield (g)

Ic

to 16 239 (20) 90 one 34.4 600 - - 8 -

IIc

b one 791 (100) 90 0.5 275 600 - 25 g twenty 42

III

C 32 377 (40) 90 2 34.4 1200 twenty - 25 -

IV

C 2 791/2170 (100/300) 90 2 550 1200 - - 2. 3 69.5

* a = Cp2 ZrCl2, b = Cp ((Me5) Cp) ZrCl2, c = (C5 Me4 SiMe2 NC12H23) TiCl2 ** MAO = 10% methylalumoxane by weight in toluene

Claims (8)

1. A composition of matter comprising ethylene polymer chains, which are copolymers in which the comonomer is C3-C12 α-olefin, and the polymer chains of ethylene have an Mn of 1,500 to 50,000, a molecular weight distribution per gel permeability chromatography (145 ° C) and index differences 5 refraction of 2 to 4, a ratio of vinyl groups to total olefin groups according to the formula (1) vinyl groups ≥ [mole percent of comonomer ÷ 0.1] a x 10a x b  olefinic groups in which, a = -0.24 and b = 0.8, and in which the total number of vinyl groups per 1000 carbon atoms is greater or equal to 8000 ÷ Mn, taking measurements of vinyl groups by gel permeation chromotography (145 ° C) and 10 1 H-NMR (125 ° C), the polymer chains of ethylene can be obtained by a method that involves contacting one or more olefin monomers with a catalyst solution composition containing a transition metal catalyst compound and an alumoxane where The ratio between aluminum and transition metal is from 10: 1 to 100: 1.

The composition of claim 1, wherein a = -0.20.

3.

The composition of claim 1, wherein a = -0.18 and b = 0.83.

Four.

The composition of claim 1, wherein a = -0.15 and b = 0.83.

5.

A branched polymer comprising branches derived from polymer chains of ethylene, which are copolymers in which the comonomer is C3-C12 α-olefin, and the polymer chains of ethylene have a Mn of

20 1,500 to 75,000, and a ratio of vinyl groups to total olefinic groups according to the formula

(1) vinyl groups ≥ [mole percent of comonomer ÷ 0.1] a x 10a x b olefinic groups in which a = -0.24 and b = 0.8 and that has a total number of vinyl groups per 1000 carbon atoms that is greater than or equal to 8000 ÷ Mn.

6.

The branched polymer of claim 5, wherein a = -0.20.

7.

The branched polymer of claim 5, wherein a = -0.18 and b = 0.83.

8.

The branched polymer of claim 5, wherein a = -0.15 and b = 0.83.

9. The branched polymer of claim 5, wherein the Mn of said olefinic polymer chains is less than or equal to 50,000 Daltons.